Herbicidal aminosulfenamide derivatives of N-phosphonomethylglycine triesters

ABSTRACT

This invention relates to aminosulfenamide derivatives of N-phosphonomethylglycine triesters which are useful as herbicides and a process for preparing these compounds. This invention further relates to herbicidal compositions containing such derivatives and to herbicidal methods employing such compounds and compositions.

This invention relates to aminosulfenamide derivatives of N-phosphonomethylglycine triesters which are useful as herbicides and a process for preparing these compounds. This invention further relates to herbicidal compositions containing such derivatives and to herbicidal methods employing such compounds and compositions.

U.S. Pat. No. 4,120,689 issued to Gerard A. Dutra on Oct. 17, 1978 discloses alkyl-[di(benzyl) or di(aryl)] esters of N-phosphonomethyl glycine prepared by the reaction of a dibenzyl or diaryl phosphite with an N-methylene lower alkyl glycinate trimer. These esters and the hydrolysis products thereof containing at least one benzyloxy or aryloxy group bonded to the phosphorus atom thereof are disclosed as compounds having the formula ##STR1## wherein R of U.S. Pat. No. 4,120,689, supra is disclosed as a member of the group consisting of phenyl, benzyl, naphthyl, biphenylyl, benzyloxyphenyl and phenyl, benzyl or naphthyl groups substituted with from 1 to 3 groups selected from the class consisting of hydroxyl, lower alkyl, lower alkoxy, lower alkylthio, trifluoromethyl, carbo (lower alkoxy), nitro, or halo; R₁ of U.S. Pat. No. 4,120,689, supra is hydrogen or an R group, and R₂ of U.S. Pat. No. 4,120,689, supra is a lower alkyl group or hydrogen and the strong acid salts of the compounds wherein neither R₁ or R₂ is H. A post-emergent herbicide utility is disclosed.

In accordance with the present invention, aminosulfenamide derivatives of N-phosphonomethylglycine of the formula ##STR2## wherein n is an integer 1 or 2 and wherein R is selected from the group consisting of phenyl, naphthyl, or biphenylyl; or phenyl, naphthyl or biphenylyl substituted with from 1 to 3 substituents independently selected from the group consisting of lower alkyl, lower alkoxy, lower alkylthio, alkoxycarbonyl, methylenedioxy, trifluoromethyl, cyano, nitro and halogen; and wherein R₁ and R₂ are independently selected from the group consisting of hydrogen, cycloalkyl, alkyl, alkyl substituted with 1 or 2 substituents independently selected from the group consisting of lower alkoxy, lower alkylthio, cyano, lower alkoxycarbonyl, bis(aryloxy)phosphinyl wherein said aryl portion thereof corresponds to a group selected from R; phenyl or phenyl substituted with 1 or 2 independently selected from the group consisting of lower alkyl and lower alkoxy; acyl or aroyl; or R₁ and R₂ are independently selected from the aforerecited groups and joined together to form a cyclic structure having 3-8 atoms therein and R₃ is lower alkyl or aralower alkyl and are prepared by reacting a compound of the formula ##STR3## wherein R and R₃ are as aforedefined with sulfur dichloride in an aprotic solvent and in the presence of a hydrogen chloride acceptor to form a compound of the formula ##STR4## wherein R and R₃ are as aforedefined.

It is preferred to add a compound of formula (II) to the sulfur dichloride rather than vice versa so as to minimize the possibility of having excess compound of formula (II) in the presence of sulfur dichloride whereby bis glyphosate adduct, an undesired coproduct could be formed.

The reaction temperature for the aforerecited reaction is in the range from about -50° C. to about 100° C., and is preferably from about -20° C. to about +30° C., although greater or lower temperatures may be employed if desired.

In preparing the compounds of formula (III), the ratio of reactants of formula (II) and sulfur dichloride, is not narrowly critical. For best results, however, for each mole of a compound of formula (II), one should employ one mole of sulfur dichloride to produce one mole of a compound of formula (III). It is preferred to employ an excess of sulfur dichloride for ease of reaction and maximum yield of product of formula (III). The 2:1 adduct byproduct and an amine hydrochloride formed along with a compound of formula (III) are generally separated therefrom as a precipitate.

The compound of formula (III) is reacted with a compound of the formula ##STR5## wherein R₁ and R₂ are as aforedefined, in the presence of a hydrogen chloride acceptor in an aprotic solvent to form a compound of formula (I).

In reacting a compound of formula (III) with a compound of formula (IV), the temperature is in the range from about -50° C. to about 100° C. and is preferably from about -20° C. to about +30° C. although greater or lower temperatures may be employed if desired.

The ratio of compounds of formula (III) and (IV) is not critical. For best results, however, one should employ for each mole of a compound of formula (III) a mole of a compound of formula (IV). Typically a molar excess of compound of formula (IV) is employed.

Typical compounds which may be employed as a compound of formula (IV) include amine compounds such as dimethylamine, diisopropylamine, diethylamine, di-n-butylamine, diphenylamine, piperidine, morpholine, thiomorpholine, glycine, [(diphenoxyphosphinyl)methyl]-, methyl ester and the like.

It is preferred that R is phenyl or phenyl substituted with lower alkoxy in the ortho or para position. R₁ and R₂ are independently preferably alkyl such as methyl, isopropyl, n-butyl, cyclic such as morpholino or piperidino, or aryl such as phenyl. R₃ is preferably lower alkyl or aralower alkyl.

Illustrative of the substituted phenyl groups which R, R₁ and R₂ independently represent are mono-substituted phenyl wherein the substituent is in the ortho, meta or para position, for example, methylphenyl, butylphenyl, methoxyphenyl, butoxyphenyl, fluorophenyl, chlorophenyl, bromophenyl, iodophenyl, trifluoromethylphenyl, nitrophenyl, methylthiophenyl, butylthiophenyl, cyanophenyl, ethoxycarbonylphenyl, and the like, and the di- and tri-substituted phenyl groups wherein the substituents are the same or different and are located in the 2, 3, 4, 5 or 6 positions of the phenyl ring, for example, dichlorophenyl, dimethylphenyl, methylchlorophenyl, ethylfluorophenyl, dibutoxyphenyl, butylnitrophenyl, methylthiochlorophenyl, di(ethylthio)phenyl, trimethylphenyl, trichlorophenyl, tributylphenyl, ethyldichlorophenyl and the like.

Groups representative of a substituted naphthyl groups represented by R include methylnaphthyl, nitronaphthyl, bromonaphthyl, dimethylnaphthyl, difluoronaphthyl, trimethylnaphthyl and the like.

Groups illustrative of substituted biphenylyl represented by R include methylbiphenylyl, nitrobiphenylyl, bromobiphenylyl, dimethylbiphenylyl, difluorobiphenylyl, trimethylyl and the like.

As employed herein, the term "lower alkyl" designates alkyl radicals which have from 1 to 4 carbon atoms in a straight or branched chain, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, and t-butyl.

The term "aralower alkyl" includes combinations of those groups as aforedefined for the term "lower alkyl" with aryl groups such as phenyl, benzyl, naphthyl and biphenylyl.

The term "halo" or "halogen" as employed herein means chlorine, bromine, iodine and fluorine.

The term "lower alkoxy" includes groups representative of the term "lower alkyl" in combination with oxygen and includes methoxy, ethoxy, propoxy, butoxy mixtures thereof and the like.

The term "lower alkylthio" includes representatives of lower alkyl in combination with sulfur.

The term "lower alkoxycarbonyl" includes groups representative of the aforedefined term "lower alkoxy" in combination with a carbonyl group.

The term "alkyl" is employed throughout the claims and description to mean a substituted or unsubstituted monovalent radical in a straight or branched chain of the formula C_(n) H_(2n+1-) derived from an aliphatic hydrocarbon by removal of one hydrogen therefrom wherein n is an integer from 1 to 8.

The term "acyl" is employed throughout the claims and description to mean an organic radical derived from an organic acid by removal of the hydroxy group and is of the form ##STR6## wherein R¹ is alkyl as defined herein.

The term "aralower alkyl" includes combinations of groups as aforedefined for the term "lower alkyl" with aryl groups such as phenyl, benzyl, naphthyl and biphenylyl.

The term "aroyl" is employed throughout the claims and description to mean a radical of the formula ##STR7## wherein R¹ is aryl, phenyl, naphthyl, biphenyl etc. as aforedefined herein.

Typical groups representative of the term "alkyl" includes groups representative of the term "lower alkyl" as well as groups such as n-pentyl, n-hexyl, n-heptyl, n-octyl, isopentyl, neopentyl, isohexyl, 2-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl and the like.

Typical groups representative of the embodiment wherein R₁ and R₂ are joined together to form a cyclic arrangement include morpholino, piperidino, thiomorpholino, phthalimido and the like.

The term "cycloalkyl" is employed throughout the claims and description to mean carbon and hydrogen atoms arranged in a cyclic or ring arrangement having 3 to 8 carbon atoms therein. Typical groups representative of the term "cycloalkyl" include cyclopentyl, cyclohexyl, cyclopropyl, cyclooctyl and the like.

The hydrogen chloride acceptor is typically an amine, preferably a tertiary amine, which will not react with the reactants employed or products formed. Examples of suitable tertiary amine hydrogen chloride acceptors include trimethylamine, triethylamine, tributylamine, trihexylamine, 1,5-diazabicyclo-[5.4.0]-undec-5-ene, pyridine, quinoline, mixtures thereof and the like.

Due to the reactive nature of the various reaction intermediates and reactants, the process of the present invention should be conducted in an aprotic solvent under essentially anhydrous conditions. Illustrative of the aprotic solvents employed in the process of this invention include benzene, toluene, methylene chloride, tetrahydrofuran, cyclohexane, methylcyclohexane, hexane, octane, dioxane, ethyl ether, mixtures thereof and the like, although a solvent is not necessary.

While the processes of this invention can be conducted at atmospheric, sub-atmospheric or super-atmospheric pressure, for convenience and economy it is generally preferred to conduct these processes at atmospheric pressure.

Also in accordance with this invention, compound of formula (I) are prepared by a process comprising reacting a compound of the formula ##STR8## wherein R and R₃ are as aforedefined with a compound of the formula ##STR9## wherein R₁ and R₂ are as aforedefined in an aprotic solvent in the presence of a hydrogen chloride acceptor, to form compounds of formula (I).

The temperatures of the aforedescribed reaction is in the range from about -50° C. to about 100° C. and preferably from about -20° C. to about +30° C., although greater or lesser temperatures may be emloyed if desired.

The molar ratio of compounds of formula (II) to compounds of formula (V) is not narrowly critical. For best results, one should employ for each mole of a compound of formula (II), one mole of a compound of formula (V). Typically an excess of compound of formula (V) is employed.

Typical compounds which may be employed as compounds of the formula R₁ R₂ NSCl include those compound such as N,N disubstituted aminosulfenyl chlorides, wherein R₁ R₂ N is morpholino, piperidino, diaryl, dialkyl wherein alkyl is as aforedefined and the like.

The preparation of the aforedescribed and other N,N disubstituted aminosulfenyl chlorides is described in Chemical Abstracts Volume 57 page 13771, Badische Anilin & Soda--Fabrik A. G., Gunther Weise and Gerhard Schulze, noting Ger. 1,132,222 both of which are incorporated by reference herein in their entirety.

The following illustrative, non-limiting examples will serve to further demonstrate to those skilled in the art the process of this invention in which specific compounds within the scope of this invention can be prepared. In the examples, all parts are parts by weight unless otherwise expressly stated.

EXAMPLE I

Glycine, N-[[bis(4-methoxyphenoxy)phosphinyl]methyl]-N-(4-morpholinylthio)-, ethyl ester corresponding to a compound formula (I) wherein n is 1, R is p-methoxyphenyl, R₃ is ethyl, and R₁ and R₂ are joined together to form a heterocyclic ring, morpholino. An oven-dried 500 ml 2-necked flask was cooled under nitrogen and charged with glycine, N-[[(bis p-methoxyphenyl)phosphinyl]methyl]-, ethyl ester (7 g, 0.0186 mol), triethylamine (1.9 g, 0.0186 mol) and 250 ml of toluene. This solution was cooled in an ice bath and the methylene chloride solution of morpholine N-sulfenyl chloride (8 g, 0.055 mol) was added via double ended needle. Preparation of morpholino N-sulfenyl chloride was via the method of German Pat. No. 1,132,222 supra. The reaction mixture was stirred for 2 hours, allowing to slowly warm to room temperature. The triethylamine hydrochloride was removed by filtration, and the filtrate was washed with cold 10% aqueous NaOH followed by cold water, dried over MgSO₄, filtered, and concentrated to 14.2 g of yellow oil. The oil was adsorbed onto 20 g of silica gel and purified by HPLC on a 1"×4' column of silica gel to give the desired product as a yellow oil, N_(D) ²⁴.3 =1.5461, in 53% yield. ¹ H NMR, ³¹ P NMR, and elemental analysis were consistent with pure product.

Calculated for: C₂₃ H₃₁ N₂ O₈ P₁ S₁ : C,52.47; H,5.93; N,5.32; S,6.10; Found: C,52.25; H,5.99; N,5.32; S,5.95.

General Procedure For The Preparation Of Aminosulfenamide Derivatives Of Glyphosate Triesters For Examples II, III & IV

An oven dried 1 liter flask was cooled under nitrogen and charged with sulfur dichloride and 300 ml of toluene. This solution was cooled to -20° C. and to it was added a toluene solution of the appropriate compound of formula (II) and triethylamine at such a rate that the temperature did not exceed -5° C. The yellow reaction mixture was stirred at -20° C. for 31/2 hours. The supernatant liquid was removed under nitrogen and concentrated to an oil. A toluene solution of the oil was added slowly to a solution of the appropriate amine and triethylamine in toluene at 5° C., maintaining the temperature below 10° C. The yellow reaction mixture was stirred for 2-4 hours, allowing to slowly warm to room temperature. The triethylamine hydrochloride was removed by filtration and the toluene filtrate was washed with cold 10% aqueous NaOH and cold water, dried over MgSO₄, and concentrated to an oil. HPLC purification gave the desired product. ¹ H NMR, ³¹ P NMR, and elemental analysis were consistent with pure products.

EXAMPLE II

The compound prepared according to the aforerecited general procedure was glycine, N-[[bis-(1-methylethyl)amino]thio]-N-[(diphenoxyphosphinyl)methyl]-, methyl ester corresponding to a compound of formula (I) wherein n is 1, R is phenyl, R₃ is methyl, and R₁ and R₂ are both isopropyl as a yellow oil having a refractive index n_(D) ²².8 of 1.5344, and having an analysis for C₂₂ H₃₁ N₂ O₅ PS:

Calculated: C,56.64; H,6.70; N,6.00; S,6.87; Found: C,56.52; H,6.73; N,5.98; S,6.83.

EXAMPLE III

The compound prepared herein according to the aforerecited general procedure was glycine, N-[(diphenoxyphosphinyl)methyl]-N-[(diphenylamino)thio]-, phenylmethyl ester corresponding to a compound of formula (I) wherein n is 1, R, R₁ and R₂ are each phenyl, and R₃ is phenylmethyl, as a yellow oil having a refractive index n_(D) ²².4 =1.6033 and an analysis for C₃₄ H₃₁ N₂ O₅ PS:

Calculated: C,66.87; H,5.12; N,4.59; S,5.25; Found: C,65.92; H,5.25; N,4.51; S,5.15.

EXAMPLE IV

The compound prepared herein according to the aforerecited general procedure was glycine, N-[[bis(2-methoxyphenoxy)phosphinyl]methyl]-N-(1-piperidinylthio)-, methyl ester corresponding to a compound of formula (I) wherein n is 1, R is 2-methoxyphenyl, R₃ is methyl, and R₁ and R₂ are joined together to form a heterocyclic ring, piperidinyl as a yellow oil having a refractive index n_(D) ²¹.8 =1.5487 and an analysis for C₂₃ H₃₁ N₂ O₇ PS:

Calculated: C,54.11; H,6.12; N,5.49; S,6.28; Found: C,53.93; H,6.14; N,5.44; S,6.31.

General Procedure For The Preparation Of Aminosulfenamides Derivatives Of Glyphosate Triesters Of Examples V and VI

An oven-dried 500 ml flask cooled under nitrogen was charged with 200 ml of toluene, cooled to -20° C. and the sulfur dichloride was added. To it was added slowly via cannula a solution of glycine, N-[(diphenoxyphosphinyl)ethyl]-, methyl ester and triethylamine in toluene, maintaining the temperature below -10° C. The reaction mixture was stirred for 1-3 hours at -20° C. The triethylamine hydrochloride was removed under nitrogen and the supernatant liquid was added slowly via cannula to a solution of the appropriate amine and triethylamine in toluene at either 0° C. or -20° C. The reaction mixture was stirred overnight at room temperature. The triethylamine hydrochloride was removed by filtration, and the filtrate was washed with cold 10% aqueous NaOH followed by cold water, dried over MgSO₄, filtered and concentrated in vacuo to an oil. Purification by HPLC on a Waters Prep Pak 500 silica gel column, eluting with 10-35% ethyl acetate/cyclohexane gave the desired products. ¹ H NMR, ³¹ NMR, and elemental analyses were all consistent with pure products.

EXAMPLE V

Glycine, N-[(dibutylamino)thio]-N-[(diphenoxyphosphinyl)methyl]-, ethyl ester was prepared per the aforerecited general procedure as a light brown oil, corresponding to a compound of formula (I) wherein n is 1, R is phenyl, R₁ and R₂ are each n-butyl and R₃ is ethyl having a refractive index n_(D) ²².6 =1.5248 and an analysis for C₂₅ H₃₇ N₂ O₅ PS:

Calculated: C,59.03; H,7.33; N,5.51; S,6.30; Found: C,58.78; H,7.25; N,5.44; S,6.51.

EXAMPLE VI

Glycine, N-[(dimethylamino)thio]-N-[(diphenoxyphosphinyl)methyl]-, ethyl ester was prepared according to the aforerecited general procedure as a yellow oil corresponding to a compound of formula (I) wherein n is 1, R is phenyl, R₁ and R₂ are each methyl, and R₃ is ethyl having a refractive index n_(D) ²².5 =1.5437 and an analysis for C₁₉ H₂₅ N₂ O₅ PS:

Calculated: C,53.77; H,5.94; N,6.60; S,7.55; Found: D,53.24; H,5.74; N,6.09; S,8.06.

EXAMPLE VII

Glycine, N,N'-thiobis[N-[(diphenoxyphosphinyl]methyl]-, dimethyl ester corresponding to a compound of formula (I) wherein n is 1, R is phenyl, R₁ is diphenylphosphonomethyl, R₂ is carbomethoxymethyl and R₃ is methyl. An oven-dried 500 ml flask, cooled under nitrogen was charged with glycine, N-[(diphenoxyphosphinyl)methyl]-, methyl ester (7.1 g, 0.021 mol), triethylamine (2.2 g, 0.021 mol) and 250 ml of toluene and cooled to 0° C. To this solution was added via double ended needle, a solution of freshly distilled sulfur dichloride (1.1 g, 0.011 mol) in toluene at such a rate to maintain the reaction temperature below 10° C. The reaction mixture was stirred for 2 hours, allowing to slowly warm to room temperature. The triethylamine hydrochloride was removed by filtration, and the filtrate was washed with cold 10% aqueous NaOH and cold water, dried over MgSO₄, filtered, and adsorbed onto 20 g of silica gel. Purification by HPLC on a 1"×4' column of silica gel gave the desired product as a yellow oil, N_(D) ²⁴.6 =1.5630, in 26% yield. ³¹ P NMR, ¹ H NMR, and elemental analysis were consistent with pure product having an analysis

Calculated for C₃₂ H₃₄ N₂ O₁₀ P₂ S₁ : C,54.86; H,4.89; N,4.00; S,4.58; Found: C,54.76; H,4.95; N,3.99; S,4.56.

EXAMPLE VIII

The post-emergence herbicidal activity of some of the various compounds of this invention was demonstrated by greenhouse testing in the following manner. A good grade of top soil is placed in aluminum pans having holes in the bottom and compacted to a depth of 0.95 to 1.27 cm. from the top of the pan. A predetermined number of seeds of each of several dicotyledonous and monocotyledonous annual plant species and/or vegetative propagules for the perennial plant species are placed on the soil and pressed into the soil surface. The seeds and/or vegetative propagules are covered with soil and leveled. The pans are then placed on a sand bench in the greenhouse and watered from below as needed. After the plants reach the desired age (two to three weeks), each pan except for the control pans is removed individually to a spraying chamber and sprayed by means of an atomizer operating at a positive air pressure of approximately 1.46 kg/cm² absolute. The atomizer contains 6 ml. of a solution or suspension of the chemical. In that 6 ml., is an amount of a cyclohexanone emulsifying agent mixture to give a spray solution or suspension which contains about 0.4% by weight of the emulsifier. The spray solution or suspension contains a sufficient amount of the candidate chemical in order to give application rates corresponding to those set forth in the tables. The spray solution is prepared by taking an aliquot of a 1.0% by weight stock solution or suspension of the candidate chemical in an organic solvent such as acetone or tetrahydrofuran or in water. The emulsifying agent employed is a mixture comprising 35 weight percent butylamine dodecylbenzene sulfonate and 65 weight percent of a tall oil ethylene oxide condensate having about 11 moles of ethylene oxide per mole of tall oil. The pans are returned to the greenhouse and watered as before and the injury to the plants as compared to the control is observed at approximately two and four weeks as indicated in the tables under WAT and the results recorded. In some instances, the two-week observations are omitted.

The post-emergence herbicidal activity index used in Table I is as follows:

    ______________________________________                                         Plant Response  Index                                                          ______________________________________                                         0-24% control   0                                                              25-49% control  1                                                              50-74% control  2                                                              75-99% control  3                                                              100% control    4                                                              ______________________________________                                    

The plant species utilized in these tests are identified by letter in accordance with the following legend:

    ______________________________________                                         A -- Canada Thistle*                                                                              K -- Barnyardgrass                                          B -- Cocklebur     L -- Soybean                                                C -- Velvetleaf    M -- Sugar Beet                                             D -- Morningglory  N -- Wheat                                                  E -- Lambsquarters O -- Rice                                                   F -- Smartweed     P -- Sorghum                                                G -- Yellow Nutsedge*                                                                             Q -- Wild Buckwheat                                         H -- Quackgrass*   R -- Hemp Sesbania                                          I -- Johnsongrass* S -- Panicum Spp                                            J -- Downy Brome   T -- Crabgrass                                              ______________________________________                                          *Established from vegetative propagules.                                       A dash (--) in the tables indicates that the particular species was absen      in the test.                                                             

                                      TABLE I                                      __________________________________________________________________________     Compound of   Plant Specifies                                                  Example No.                                                                           WAT kg/h                                                                              A B C D E F G H I J K                                            __________________________________________________________________________     I      4   11.2                                                                              2 3 1 2 3 4 2 1 1 0 3                                                   4   5.6                                                                               3 2 2 2 3 2 2 1 3 1 3                                            II     4   11.2                                                                              1 4 3 3 3 3 3 4 3 2 4                                                   4   5.6                                                                               4 3 3 2 4 3 2 4 2 2 4                                            III    4   11.2                                                                              2 2 1 2 3 3 2 2 0 0 2                                                   4   5.6                                                                               0 1 0 1 3 0 1 0 0 1 1                                            IV     4   11.2                                                                              4 4 3 2 3 4 1 4 2 2 4                                                   4   5.6                                                                               4 3 4 3 4 4 2 1 1 3 4                                            V      4   11.2                                                                              4 3 3 4 4 3 3 4 4 3 3                                                   4   5.6                                                                               2 3 3 2 3 2 3 3 3 3 4                                            VI     4   11.2                                                                              4 4 3 3 3 4 3 4 4 3 4                                                   4   5.6                                                                               4 4 3 3 4 4 3 4 3 3 4                                            VII    4   11.2                                                                              3 3 3 2 3 4 2 1 3 2 3                                                   4   5.6                                                                               1 3 1 1 3 3 2 2 1 1 3                                            __________________________________________________________________________

                                      TABLE II                                     __________________________________________________________________________     Compound of    Plant Species                                                   Example No.                                                                           WAT kg/h                                                                               L M N O P B Q D R E F C J S K T                                 __________________________________________________________________________     I      4   5.6 2 3 3 2 3 3 4 3 2 4 3 4 3 4 4 4                                        4   1.12                                                                               1 1 1 1 2 2 1 2 3 2 1 1 1 3 3 3                                        4   0.28                                                                               0 0 1 0 1 0 0 1 0 3 0 1 0 1 1 3                                 II     4   5.6 4 3 4 4 4 4 4 4 3 3 4 3 4 4 4 4                                        4   1.12                                                                               3 3 2 3 2 2 1 2 1 2 3 2 2 2 3 3                                        4   0.28                                                                               0 1 1 0 1 1 0 0 0 3 2 1 1 2 2 3                                        2   0.056                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                 III    4   5.6 2 3 1 3 3 3 3 2 2 3 2 1 2 3 4 3                                        4   1.12                                                                               1 2 0 0 0 2 1 1 0 3 2 1 0 1 1 2                                        2   0.28                                                                               0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                 IV     4   5.6 2 2 2 2 2 3 2 2 3 4 4 3 2 3 3 4                                        4   1.12                                                                               1 1 1 0 1 1 1 2 2 3 3 2 0 1 3 3                                        2   0.28                                                                               0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                        2   0.056                                                                              0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0                                 V      4   5.6 2 4 4 3 4 3 3 1 4 4 --                                                                               3 3 4 4 4                                        4   1.12                                                                               2 3 2 3 3 3 3 1 2 3 --                                                                               2 3 4 4 4                                        4   0.28                                                                               0 1 0 0 2 2 1 0 1 --                                                                               --                                                                               3 1 1 2 3                                        2   0.056                                                                              0 0 0 0 1 1 0 1 0 0 --                                                                               1 0 0 2 3                                 VI     4   5.6 2 2 3 2 3 3 3 3 3 3 --                                                                               2 3 3 3 4                                        4   1.12                                                                               0 2 2 0 0 0 0 0 0 0 --                                                                               0 0 0 0 0                                        2   0.28                                                                               0 0 0 0 0 0 0 0 1 1 --                                                                               0 0 0 0 0                                        2   0.056                                                                              0 0 0 0 0 0 0 0 0 0 --                                                                               0 0 0 0 0                                        2   0.0112                                                                             0 0 0 0 0 0 0 0 0 0 --                                                                               0 0 0 0 0                                 __________________________________________________________________________

EXAMPLE IX

The pre-emergent herbicidal activity of various compounds of this invention is demonstrated as follows. A good grade of top soil is placed in aluminum pans and compacted to a depth of 0.95 to 1.27 cm. from the top of each pan. A predetermined number of seeds or vegetative propagules of each of several plant species are placed on top of the soil in each pan and then pressed down. Herbicidal compositions prepared as in the previous example are applied by admixture with or incorporation in the top layer of soil.

In this method, the soil required to cover the seeds and propagules is weighed and admixed with a herbicidal composition containing a known amount of the active ingredient (compound of this invention). The pans are then filled with the admixture and leveled. Watering is carried out by permitting the soil in the pans to absorb moisture through apertures in the pan bottoms. The seed and propagule containing pans are placed on a wet sand bench and maintained for approximately two weeks under ordinary conditions of sunlight and watering. At the end of this period, the number of emerged plants of each species is noted and compared to an untreated control. The data is given in Table III.

The pre-emergent herbicidal activity index used below is based upon average percent control of each species as follows:

    ______________________________________                                         Percent Control  Index                                                         ______________________________________                                         0-24% control    0                                                             25-49% control   1                                                             50-74% control   2                                                             75-100% control  3                                                             ______________________________________                                    

Plant species in the table are identified by the same code letters used in the previous example.

                                      TABLE III                                    __________________________________________________________________________     Compound of   Plant Species                                                    Example No.                                                                           WAT kg/h                                                                              A B C D E F G H I J K                                            __________________________________________________________________________     I      2   11.2                                                                              3 0 0 0 3 0 0 1 0 0 2                                            II     2   11.2                                                                              3 0 0 0 0 0 0 0 0 0 0                                            III    2   11.2                                                                              0 0 0 0 0 0 0 0 0 0 0                                            IV     2   11.2                                                                              2 0 0 0 2 0 0 0 1 0 0                                            V      2   11.2                                                                              3 0 0 0 0 --                                                                               0 2 0 0 1                                            VI     2   11.2                                                                              2 0 0 0 0 --                                                                               1 0 3 0 0                                            VII    2   11.2                                                                              2 0 0 0 0 0 0 0 0 0 0                                            __________________________________________________________________________

From the test results presented in Tables I and II, it can be seen that the post-emergent herbicidal activity of the compounds of this invention is, for the most part, general in nature. In certain specific instances, however, some selectivity is demonstrated. In this regard it should be recognized that each individual species selected for the above tests is a representative member of a recognized family of plant species.

From Table III, it can be seen that the pre-emergent herbidical activity demonstrated some selectivity.

The herbicidal compositions, including concentrates which require dilution prior to application to the plants, of this invention contain from 5 to 95 parts by weight of at least one compound of this invention and from 5 to 95 parts by weight of an adjuvant in liquid or solid form, for example, from about 0.25 to 25 parts by weight of wetting agent, from about 0.25 to 25 parts by weight of a dispersant and from 4.5 to about 94.5 parts by weight of inert liquid extender, e.g., water, acetone, tetrahydrofuran, all parts being by weight of the total composition. Preferably, the compositions of this invention contain from 5 to 75 parts by weight of at least one compound of this invention, together with the adjuvants. Where required, from about 0.1 to 2.0 parts by weight of the inert liquid extender can be replaced by a corrosion inhibitor such as ethanol mercaptan, sodium thiosulfate, dodecylmono or dimercaptan or anti-foaming agent such as a dimethylpolysiloxane, or both. The compositions are prepared by admixing the active ingredient with an adjuvant including diluents, extenders, carriers and conditioning agents to provide compositions in the form of finely-divided particulate solids, pellets, solutions, dispersions or emulsions. Thus, the active ingredient can be used with an adjuvant such as a finely-divided solid, a liquid of organic origin, water, a wetting agent, a dispersing agent, an emulsifying agent or any suitable combination of these.

The herbicidal compositions of this invention, particularly liquids and soluble powders, preferably contain as a conditioning agent one or more surface-active agents in amounts sufficient to render a given composition readily dispersible in water or in oil. The incorporation of a surface-active agent into the compositions greatly enhances their efficacy. By the term "surface-active agent", it is understood that wetting agents, dispersing agents, suspending agents and emulsifying agents are included therein. Anionic, cationic and nonionic agents can be used with equal facility.

Preferred wetting agents are alkyl benzene and alkyl naphthalene sulfonates, sulfated fatty alcohols, amines or acid amides, long chain acid esters of sodium isothionate, esters of sodium sulfosuccinate, sulfated or sulfonated fatty acid esters petroleum sulfonates, sulfonated vegetable oils, polyoxyethylene derivatives of phenols and alkylphenols (particularly isooctylphenol and nonylphenol) and polyoxyethylene derivatives of the mono-higher fatty acid esters of hexitol anhydrides (e.g., sorbitan). Preferred dispersants are methyl cellulose, polyvinyl alcohol, sodium lignin, sulfonates, polymeric alkyl naphthalene sulfonates, sodium naphthalene sulfonate, polymethylene bisnaphthalenesulfonate and sodium N-methyl-N-(long chain acid) taurates.

When operating in accordance with the present invention, effective amounts of the compounds or compositions of this invention are applied to the plants, or to soil containing the plants, or are incorporated into aquatic media in any convenient fashion. The application of liquid and particulate solid compositions to plants or soil can be carried out by conventional methods, e.g., power dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray because of their effectiveness at low dosages. The application of herbicidal compositions to aquatic plants is usually carried out by adding the compositions to the aquatic media in the area where control of the aquatic plants is desired.

The application of an effective amount of the compounds or compositions of this invention to the plant is essential and critical for the practice of the present invention. The exact amount of active ingredient to be employed is dependent upon the response desired in the plant as well as such other factors as the plant species and stage of development thereof, and the amount of rainfall as well as the specific glycine employed. In foliar treatment for the control of vegetative growth, the active ingredients are applied in amounts from about 0.112 to about 56.0 or more kilograms per hectare. In pre-emergent treatments, the rate of application can be from about 5.6 to about 22.4 or more kilograms per hectare. In applications for the control of aquatic plants, the active ingredients are applied in amounts of from about 1.0 parts per million to about 1000 parts per million, based on the aquatic medium. An effective amount for phytotoxic or herbicidal control is that amount necessary for overall or selective control, i.e., a phytotoxic or herbicidal amount. It is believed that one skilled in the art can readily determine from the teachings of this specification, including examples, the approximate application rate.

There are several possible methods for applying liquid compositions of this invention to emerged plants. Such methods include the use of wiper systems whereby the plant to be treated is contacted with an absorbent material containing the particular liquid composition, a portion of which is thereby released onto the plant upon contact therewith. Such wiper systems typically comprise a reservoir of the liquid composition into which a portion of the absorbent material is placed and is fed therethrough. Generally, substances employable as absorbent material include substances of any shape or form capable of absorbing the liquid composition and releasing a portion of the same upon contact with the plant. Typical absorbent materials include felt, foam rubber, cellulose, nylon, sponges, hemp, cotton, burlap, polyester over acrylic, combinations thereof and the like. Forms of absorbent material include rope, twine, string, cloths, carpets, combinations thereof and the like. These forms may be assembled in any manner desired including a pipe rope wick, a wedge rope wick, a multi-rope wick and the like.

In another possible application method, liquid compositions may be selectively applied to weeds by the use of recirculating sprayer systems wherein the recirculating spray unit is mounted on a tractor or high clearance mobile equipment and the spray is directed horizontally onto the weeds growing over a crop. Spray not intercepted by the weeds is collected in a recovery chamber before contacting the crop and is reused. Roller applications may also be employed to apply liquid compositions to weeds growing over a crop.

In yet another possible application method, shielded applicators may be employed to direct the liquid composition in the form of a spray onto the weeds while effectively shielding the crops from the spray.

These and other possible application methods for selectively applying liquid compositions to weeds are discussed in detail in Innovative Methods of Post-Emergence Weed Control, McWhorter C. G., Southern Weed Science Society, 33rd Annual Meeting Proceedings, Jan. 15-17, 1980; Auburn University Printing Service, Auburn, Ala. U.S.A., the teachings of which are incorporated herein by reference in their entirety.

Another possible method of applying liquid compositions of this invention to plants includes controlled droplet application which is also known as the ultra low-volume chemical application. Controlled droplet application involves the production of uniform or nearly PG,25 uniform spray drops of a predetermined size and the conveyance of these drops with negligible evaporation to a spray target. In particular, this method comprises feeding spray solutions to a rotary atomizer comprising a small disk with serrated edges that disperses liquid into droplets as the disk spins. Different droplet sizes are produced by changing solution flow rates to the spinning disk or changing the speed of rotation of the disk.

Those of skill in the art will recognize that the physical and chemical characteristics of the compound or composition employed will determine to a large extent the particular application method selected therewith.

The aforementioned and other methods for applying liquid compositions to plants are discussed in detail in "Rope Wick Applicator--Tool With A Future", Dale, James E., pp. 3-4, "The Recirculating Sprayer and Roundup® Herbicide", Derting, Claude W., pp. 5-7, and "C.D.A. Herbicide Application", McGarvey, Frank X., Weeds Today, Volume 11, Number 2, pp. 8-9, Late Spring, 1980, 309 W. Clark St., Champaign, Ill., the teachings of which are incorporated herein by reference in their entirety.

Although this invention has been described with respect to specific modifications, the details thereof are not to be construed as limitations, for it will be apparent that various equivalents, changes and modifications may be resorted to without departing from the spirit and scope thereof and it is understood that such equivalent embodiments are intended to be included herein. 

What is claimed is:
 1. A method of controlling undesired plants which comprises applying to said plants or plant growth medium a herbicidally effective amount of a compound of the formula ##STR10## wherein n is an integer 1 or 2 and wherein R is selected from the group consisting of phenyl, naphthyl, or biphenylyl; or phenyl, naphthyl or biphenylyl substituted with from 1 to 3 substituents independently selected from the group consisting of lower alkyl, lower alkoxy, lower alkylthio, alkoxycarbonyl, methylenedioxy, trifluoromethyl, cyano, nitro and halogen; and wherein R₁ and R₂ are independently selected from the group consisting of hydrogen, cycloalkyl, alkyl, alkyl substituted with 1 or 2 substituents independently selected from the group consisting of lower alkoxy, lower alkylthio, cyano, lower alkoxycarbonyl, bis(aryloxy)phosphinyl wherein said aryl portion thereof corresponds to a group selected from R; phenyl or phenyl substituted with 1 or 2 substituents independently selected from the group consisting of lower alkyl and lower alkoxy; acyl or aroyl; or R₁ and R₂ are independently selected from the aforerecited groups and joined together to form a cyclic structure having 4-8 atoms therein and R₃ is lower alkyl or aralower alkyl.
 2. The method of claim 1, wherein n is one.
 3. The method of claim 2, wherein R is phenyl or phenyl substituted with 1 or 2 substituents selected from the group consisting of lower alkyl, lower alkoxy and halogen.
 4. The method of claim 3, wherein R₃ is lower alkyl.
 5. The method of claim 1, wherein said compound is glycine, N-[(dimethylamino)thio]-N-[(diphenoxyphosphinyl)methyl]-, ethyl ester.
 6. The method of claim 1, wherein said compound is glycine, N-[(dibutylamino)thio]-N-[(diphenoxyphosphinyl)methyl]-, ethyl ester.
 7. The method of claim 1, wherein said compound is glycine, N-[[bis(4-methoxyphenoxy)phosphinyl]methyl)]-N-(4-morpholinylthio)-, ethyl ester.
 8. The method of claim 1, wherein R₁ and R₂ are not the same.
 9. The method of claim 1 wherein said compound is glycine, N,N-thiobis[N-[diphenoxyphosphinyl)methyl]dimethyl ester.
 10. A compound of the formula ##STR11## wherein n is an integer 1 or 2 and wherein R is selected from the group consisting of phenyl, naphthyl, or biphenylyl; or phenyl, naphthyl or biphenylyl substituted with from 1 to 3 substituents independently selected from the group consisting of lower alkyl, lower alkoxy, lower alkylthio, alkoxycarbonyl, methylenedioxy, trifluoromethyl, cyano, nitro and halogen; and wherein R₁ and R₂ are independently selected from the group consisting of hydrogen, cycloalkyl, alkyl, alkyl substituted with 1 or 2 substituents independently selected from the group consisting of lower alkoxy, lower alkylthio, cyano, lower alkoxycarbonyl, bis(aryloxy)phosphinyl wherein said aryl portion thereof corresponds to a group selected from R; phenyl or phenyl substituted with 1 or 2 substituents independently selected from the group consisting of lower alkyl and lower alkoxy; acyl or aroyl; or R₁ and R₂ are independently selected from the aforerecited groups and joined together to form a cyclic structure having 4-8 atoms therein and R₃ is lower alkyl or aralower alkyl.
 11. A compound of claim 10 wherein n is one.
 12. A compound of claim 11 wherein R is phenyl or phenyl substituted with 1 or 2 substituents selected from the group consisting of lower alkyl, lower alkoxy and halogen.
 13. A compound of claim 12 wherein R₁ and R₂ are the same.
 14. A compound of claim 13 wherein R₃ lower alkyl.
 15. A compound of claim 14 wherein said compound is glycine, N-[(dimethylamino)thio]-N-[(diphenoxyphosphinyl)methyl]-, ethyl ester.
 16. A compound of claim 14 wherein said compound is glycine, N-[(dibutylamino)thio]-N-[(diphenoxyphosphinyl)methyl]-, ethyl ester.
 17. A compound of claim 12 wherein said compound is glycine, N-[[bis(4-methoxyphenoxy)phosphinyl]methyl]-N-(4-morpholinylthio)-, ethyl ester.
 18. A compound of claim 12 wherein R₁ and R₂ are not the same.
 19. A compound of claim 18 wherein the compound is glycine, N,N'-thiobis[N-[(diphenoxyphosphinyl]methyl]-, dimethyl ester.
 20. A herbicidal composition comprising an inert adjuvant and a herbicidally effective amount of a compound of the formula ##STR12## wherein n is an integer 1 or 2 and wherein R is selected from the group consisting of phenyl, naphthyl, or biphenylyl; or phenyl, naphthyl or biphenylyl substituted with from 1 to 3 substituents independently selected from the group consisting of lower alkyl, lower alkoxy, lower alkylthio, alkoxycarbonyl, methylenedioxy, trifluoromethyl, cyano, nitro and halogen; and wherein R₁ and R₂ are independently selected from the group consisting of hydrogen, cycloalkyl, alkyl, alkyl substituted with 1 or 2 substituents independently selected from the group consisting of lower alkoxy, lower alkylthio, cyano, lower alkoxycarbonyl, bis(aryloxy)phosphinyl wherein said aryl portion thereof corresponds to a group selected from R; phenyl or phenyl substituted with 1 or 2 substituents independently selected from the group consisting of lower alkyl and lower alkoxy; acyl or aroyl; or R₁ and R₂ are independently selected from the aforerecited groups and joined together to form a cyclic structure having 4-8 atoms therein R₃ is lower alkyl or aralower alkyl.
 21. The herbicidal composition of claim 20, wherein n is one.
 22. The herbicidal composition of claim 21 wherein R is phenyl or phenyl substituted with 1 or 2 substituents selected from the group consisting of lower alkyl, lower alkoxy and halogen.
 23. The herbicidal composition of claim 22, wherein R₃ is lower alkyl.
 24. The herbicidal composition of claim 20, wherein said compound is glycine, N-[(dimethylamino)thio]-N-[(diphenoxyphosphinyl)methyl]-, ethyl ester.
 25. The herbicidal composition of claim 20, wherein said compound is glycine, N-[(dibutylamino)thio]-N-[(diphenoxyphosphinyl)methyl]-, ethyl ester.
 26. The herbicidal composition of claim 20, wherein said compound is glycine, N-[[bis(4-methoxyphenoxy)phosphinyl]methyl]-N-(4-morpholinylthio)-, ethyl ester.
 27. The herbicidal composition of claim 20, wherein R₁ and R₂ are not the same.
 28. The herbicidal composition of claim 20, wherein said compound is glycine, N,N'-thiobis[N-[(diphenoxyphosphinyl]methyl]-, dimethyl ester. 